Process for sizing textile materials

ABSTRACT

A method for sizing textile yarns which comprises coating the textile yarn with a solution of an interpolymerization product of vinyl acetate, dialkyl maleate and acrylic acid and drying the coated textile yarn to remove solvent, and textile materials sized therewith.

United States Patent 1191 Corey et al.

[ 1, Dec. 17, 1974 PROCESS FOR SIZING TEXT-ILE MATERIALS Assignee: Monsanto Company, St. Louis, Mo.

Filed: Feb. 5, 1973 Appl. No.: 329,495

Related US. Application Data Continuation-impart of Set. No. 98,915, Dec. 16, 1970, Pat. No. 3,723,381.

us. 01 ..117/139.s A, 117/161 uc,

117/161 UT, 117/161 UZ 1m. 0. .6 C08j 1/44 Field ofSearch 117/1395 A, 161 UC,

117/161 UT, 161 UZ; 260/296 TA [56] References Cited UNITED'STATES PATENTS 2,576,915 12/1951 Barrett 117/1395 A 2,651,587 9/1953 Rossin 1 117/1395 A 2,686,137 8/1954 Rossin et a1. 117/1395 A 2,799,914 7/1957 Nickerson 117/1395 A 2,808,348 10/1957 Harris 117/1395 A 2,848,357 8/1958 Harris 117/1395 A 2,855,387 10/1958 Barrett 117/1395 A Primary ExaminerWilliam D. Martin Assistant Examiner-Theodore G. Davis Attorney, Agent, or FirmR. Bruce B1ance;' Edward P. Grattan; James C. Logomasini 57 ABSTRACT A method for sizing textile yarns which comprises coating the textile yarn with a solution of an interpolymerization product of vinyl acetate, dialkyl maleate and acrylic acid and drying the coated textile yarn to remove solvent, and textile materials sized therewith.

13 Claims, N0 Drawings PROCESS FOR SIZING TEXTILE MATERIALS CROSS REFERENCE TO RELATED APPLICATIONS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to textile sizes. More particularly, it relates to poly(vinyl acetate-dialkyl maleateacrylic acid) textile sizes wherein the dialkyl maleate is selected from the group consisting of dimethyl maleate and diethyl maleate and to textiles sized with these materials.

2. The Prior Art Polymeric substances are well known in the prior art for use as textile sizes. In conventional loom operations yarn is sized with an aqueous solution of a water soluble material such as a copolymer of vinyl acetate and carboxylic acid, woven into cloth on a conventional loom with a mechanical shuttle and then the size is removed in a water bath. While these sizes have been adequate in the past, recent developments in the textile industry have created an increasing demand for textile sizes with improved tensile strength, elongation, toughness, solubility characteristics, etc.

One such development in recent years is the waterjet loom. The water jet loom employs a jet of water in place of a mechanical shuttle in order to weave the yarn into a fabric. A water jet loom provides a faster weaving operation and less mechanical abrasion of the yarn. The result is an increase in production and improved quality in the woven fabric. a

The size used in water jet weaving operations is customarily applied from aqueous solution. Once it is applied to the yarn and dried, the size must be sufficiently water resistant so as to remain on the yarn during the weaving operation. Moveover, in order to be efficient and effective, the size must retain its adhesion and film properties such as high tensile strength when wet by the water jets in the weaving process without becoming soft and slimy. Finally, the size must be soluble in mild aqueous alkali solutions or organic solvents so that it can be removed from the woven fabric. The foregoing properties are the result of a critical inter-relationship between chemical composition and molecular weight of the polymeric material which is used as the textile size.

The sizesof the prior art which are customarily used in conventional loom weaving operations are found to lack the necessary physical properties. which are required for use with water jet looms.

Thus, there exists in the art a need for improved textile sizes which can be used to size yarns which are to be woven on conventional or water jet looms and then removed using either an aqueous alkali solution or an organic solvent.

SUMMARY OF THE INVENTION The above-mentioned need in the prior art is fulfilled by the present invention which provides poly( vinyl acetate-dialkyl maleate-acrylic acid) textile sizes which are suitable for use on both conventional and water jet looms.

The textile sizes of the present invention have excellent solubility characteristics and film properties. Moreover, these sizes are easily removed from sized yarns or the resulting fabric using aqueous alkali solutions or organic solvents. Consequently, these sizes are especially suitable for use as yarn warp sizes for use on conventional or water jet looms.

THE PREFERRED EMBODIMENTS The sizes of the present invention are prepared from latices obtained by interpolymerizing vinyl acetate, a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and acrylic acid. The polymerization charge comprises from 83 to 95 percent by weight of vinyl acetate, from 2 to 10 percent by weight of dialkyl maleate and from 3 to 7 percent by ization methods at a temperature in the range of from 40 to 60 C. and preferably at a temperature inthe range of from 40 to 45 C. At temperatures below about 40 C. the polymerization rate is too slow and the reaction mass tends to coagulate. At polymerization temperatures above 60 C. the product is of low molecular weight and lacks the tensile strength and elongation required in sizes for use on water jet looms.

The interpolymerization is carried out using a surfactant which comprises an anionic phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from seven to 11 carbon atoms. Especially preferred are the phosphate esters of tertiary octyl phenol-ethylene oxide condensates (hereinafter referred to as PEOPEO) and the phosphate esters of nonyl phenol-ethylene oxide condensates (PENPEO). These preferred surfactants are available commercially as Triton XQS (Rohm & Haas Company) and GA FAC RE-870 (General Aniline & Film Company), respectively. The amount of the phosphate ester of an alkyl phenolethylene oxide condensate used will be in the range of from 1.0 to 4.0 percent by weight based on the total weight of the latex.

Preferably, the interpolymerization of the monomers is carried out using an anionic co-surfactant in combination with the phosphate esters of an alkyl phenolethylene oxide condensate. The use of the cosurfactants reduces the amount of coagulum in the resulting latex and provides a better product. The preferred cosurfactants used in the present invention includes alkyl sulfonates such as sodium dodecyl benzene sulfonate; fatty alcohol sulfates such as sodium lauryl sulfate; dialkyl sulfosuc'cinates, sodium dihexyl sulfosuccinate; etc.

The amount of co-surfactant used is in the range of 0.1 to 0.3 percent by weight and more preferably 0.15 to 0.25 percent by weight based on the total weight of the latex.

The polymerization processes are initiated by a two component redox free radical initiator system. Suitable oxidizing components for the system arethe inorganic peracid salts such as ammonium, potassium and sodium persulfates, perborates, and hydrogen peroxide. Preferred, however, are the oil soluble organic hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, etc. and esters of the t-butyl perbenzoate type. The useful reducing compone'nts include compounds like the sulfites, bisulfites, hydrosulfites and thiosulfites; ethyl and other alkyl'sulfites; the sulfoxylates, such as sodium formaldehyde su-lfoxylate; and the like. Especially preferred are initiator systems based on t-butyl hydroperoxide and sodium formaldehyde sulfoxylate; and redox combinations such as mixtures of hydrogen peroxide and an iron salt; hydrogen peroxide and zinc formaldehyde sulfoxylate or other similar reducing agent; hydrogen peroxideand a titanous salt; potassium persulfate and sodium bisulfate and a bromate mixed with a bisulfate.

The use of equimolar amounts of initiator system components is generally preferred although the amount of each component as well as the total amount of catalyst used depends on the type of component used as well as on other polymerization conditions and may range between .02 and 0.2 percent by weight of the total polymerization system, the preferred range being 0.02 to 0.06 percent for the oxidizing component and 0.04 to 0.1 percent for the reducing component.

The solids contents of the latices can be varied over a wide range. The preferred latices having a solids content in the range of from to 65 percent by weight and more preferably from 35 to 55 percent by Weight, based on the total weight of the latex.

During the polymerization reaction a conventional base such as ammonium hydroxide or sodium hydrox-' ide is used to buffer the latex-to a pH in the range of 4.0 to 6.0.

The following examples are set forth in illustration of the present invention and should not be construed as a limitation thereof. Unless otherwise indicated, all parts and percentages given are by weight and polymerization temperatures are maintained in the range of from 41 to 45 C.

PART A PREPARATION or LATlCES EXAMPLE 1 sphere and mild agitation usmg the tollowmg charge:

CHARGE PARTS A, Water 62.03 PEOPEO v 1.58 Ammonium hydroxide (287r) 0.20 Sodium formaldehyde sulfox late 0.05 B. t-but hydroperoxide (90 r) 0.03 Dimethyl maleate (DMM) 1.75 Vinyl Acetate (VOAC) 31.67 Acrylic Acid 1.58

The PEOPEO surfactant, ammonium hydroxide buffer solution, sodium formaldehyde sulfoxylate and the water are charged to a glass lined reaction vessel. The tertiary butyl hydroperoxide polymerization initiator is dissolved in the monomeric mixture and 8 percent of the monomeric charge (charge B) is then dispersed in the charge A. The remaining 92 percent of the monomers (charge B) is added to the reaction. vessel by a conventional delayed addition technique over a period of 2 /2 hours. During this time the temperature of the reaction batch is maintained in the range of from 41 to C. while maintaining mild agitation.

1 The resulting latex has a total solids of 35.7 percent, a pH of 4.9 and a Brookfield viscosity of 23 centipoises. The poly(vinyl acetate-dimethyl maleate-acrylic acid) resin has a specific viscosity of 2.51 when measured as a'l percent solution in dimethyl sulfoxide at 25 C.

Other properties of this latex are tabulated in Table 1 below.

EXAMPLES 2 TO 10 Thefollowing Examples 2 to 10 are set forth to illustrate variations in the latex polymerization reaction conditions of the present invention. in each case the TABLE l SUMMARY OF EXAMPLES 1 TO .10

EXAMPLE 1 2 3 4 5 6 7 8 9 10 Charge A Water 62.03 I 57.7 57.87 62.03 62.03 57.70 62.03 57.03 62.03 57.70 PEOPEO 1.58 1.58 1.58 1.26 1.58 1.58 PENPEO 1.58 1.58 1.58 1.58 SDS 0.20. 0.20 0.20 0 25 0.20 0.20 0.20 0.20 0.20 Nl-LOH (28%) 0.20 0.39 0.39 0 20 0.20 0.39 0.20 0 39 NaOH 0.18 0.18 Charge B Total Monomer 35 40.0 40.0 35.0 35.0 40.0 35 40 35 40 Vinyl Acetate 90.5 86.65 91.65 90.5 86.5 90.5 90.5 89.5 90.5 90.5 Dialkyl Maleate 5.0 10.0 5.0 5.0 7.5 5.0 5.0 5.0 5.0 5.0 Acrylic Acid 4.5 3.35 3.35 4.5 6.0 4.5 4.5 5.5 4.5 4.5 Total Coagulum 0.68 0.02 0.16 0.2 0.05 0.15 0.08 0.07 0.04 Polymer Properties Specific Viscosity 2.51 1.38 1.64 2.31 2.93 2.85 2.92 6.05 2,78 2.58 Tensile/% Elongation Dry R.H. 31901288 51301110 23501380 29001283 2150/320 33201370 35601423 30401360 17701442 20301310 15301430 23101541 720/590 20001574 14401470 Wet Dry R.H.

In the foregoing Table 1, percent total coagulum refers to all coagulum produced, both filterable and remaining as fouling on the impeller and walls of the reactor. This value is measured by recovering the coagulum by filtration and by scraping from the equipment, drying it, weighing it, and calculating its percent weight based on the calculated solids. Values in excess of 0.75 percent indicate that objectionable kettle fouling would occur in commercial scale batches which would cause serious problems in product yields, product handling and equipment clean-up.

Specific viscosity measurements are made on 1 percent solutions in dimethyl sulfoxide at 25 C.

Tensile (PSI) and elongation are measured according to ASTM Method D-882-67 after conditioning at 65 percent and 80 percent relative humidity. The wet values are obtained on 4 mil films which are immersed in water for 5 minutes.

Example 9 uses diethyl maleate as the dialkyl maleate component while all of the other examples use dimethyl maleate. Examples 1, 4, 5 and 7 to 9 use a phosphate ester of an octyl phenol-ethylene oxide condensate (PEOPEO) while the other exampl'es use a phosphate ester of a nonyl phenol-ethylene oxide condensate (PENPEO). Example 1 uses a single surfactant while Examples 2 to 10 use a combination of a major amount of PEOPEO or PENPEO with a minor amount of sodium dihexyl sulfosuccinate (SDS) which is available commercially as AEROSOL M.A. from American Cyanamid. Note in Examples 2 to 10 that when a combination of surfactants is used, the percent total coagulum is significantly lower than in Example 1 wherein a single surfactant is used.

Examples 1 to 4 and 7 to 10 are prepared using ammonium hydroxide as the buffer agent while Examples 5 and 6 use sodium hydroxide. The high wet tensile strength of the polymers prepared in Examples 1 to 5 and 7 to .10 using ammonium hydroxide, indicate their suitability for use as a size in a water jet weaving process.

The polymeric products of Examples 2 and'3 contain only 3.35 percent acrylic acid monomer. These polymers have good water resistance, tensile and elongation,

making these polymers very suitable for use in water jet weaving processes using organic solvent dsizing methods.

In order to be suitable for use as sizes in the water jet weaving process the polymeric suze must have a good tensile strength. toughness and adhesion to the yarn under wet conditions. The specific viscosities of the polymers of the present invention are good indices as to wet tensile strength and toughness when considered in the context of the type and amount of comonomers present in the polymer. The preferred polymers of the present invention have a specific viscosity in the range of from 1.2 to 12.0 and more preferably in the range of from 1.3 to 10.0. I

The correlation between specific viscosity of the polymers of the present invention and wet tensile strength are shown in the following Table 11 wherein five series of polymers are prepared using the general procedures of Examples 2 to 10 above. Variations in the amount of catalyst and polymerization temperatures lead to variations in the specific viscosity of the resulting polymers. These polymers are then tested for wet tensile strength and the results are tabulated in the following Table II.

tained when the polymerization reaction is in the range TABLE I1 CORRELATION OF WET TENSILE STRENGTH WI'IH SPECIFIC VISCOSITY 1) Polymers are prepared using the following 7! by weight monomer charges A vinyl acetate/dimethyl maleate/acrylic acid 9l.65/5.0/3.35

B vinyl acetate/dimethyl maleate/acrylic acid 90.5/5/4.5

C vinyl acetate/dimethyl maleate/acrylic acid /5/5 D vinyl acetate/diethyl maleate/acrylic acid 90.5/5/4.5

E vinyl acetate/dibutyl maleate/acrylic acid 9l.65/5/3.35

(2) Tensile values for C-1 and C2 are determined at 807: RH.

The data in the foregoing Table II illustrate that in a given series, using the prescribed dimethyl maleate and diethyl maleate monomers of the present invention, the

greater the specific viscosity the greater is the wet ten-' sile strength. On the other hand, Series E prepared using dibutyl maleate has very low wet tensile strength as compared to comparable polymers having approximately the same specific viscosity. In this regard attention is directed to a comparison between Series E and Series A-3, A-4, B-1 and B-2.

EXAMPLES 11 to 13 The following Examples 1 1-13 are set forth as control examples to illustrate the effect of polymerization temperature on the physical properties of the resulting 1atex. In each example the general charge and procedure of Example 10 is repeated while the polymerization temperature is varied. Thespecific viscosity of the resulting polymer is then measured. The results are tabulated in Table III below.

TABLE III SUMMARY OF EXAMPLES 11 to 13 POLYMERIZA- SPECIFIC TION- EXAMPLE TEMP.C. VISCOSITY 10 49-45 2.58 1 1 35-39 run coagulated 12 46-50 2.13 13 51-55 2.03

The data in the foregoing Table III indicates that, within the framework of the present invention polymerization temperatures below 40 C. lead to coagulation while increasing temperatures above 45 C. lead to polymers with decreasing specific viscosities. However, for any given polymer system within the framework of the present invention, optimum specific viscosity is obof from 40 to 60 C. and more preferably from 40 to 50 C.

The following Examples 14 to 19 are set forth to further illustrate the criticalities of the present invention.

EXAMPLE 14 The general charge and procedure of Example 3 is repeated here except that fumaric acid is substituted for the acrylic acid used in Example 3. The reactants are mixed and heated. No significant polymerization reaction has taken place even after 24 hours.

EXAMPLE 15 Example l4 is repeated hereexcept using crotonic acid in place of fumaric acid. The polymerization is carried out for 5% hours. At the end of this time, the

reaction mixture is found to contain 9 percent by weight of free monomer based on the total latex weight. This low conversion rate makes the polymer process unacceptable for use on a commercial scale. Moreover, the polymer is found to have a specific viscosity of only 1.1 and is unacceptable for use as a size in a water jet weaving process.

EXAMPLE 16 'wet. The low wet tensile strength of this polymer coupled with poor wet adhesion to acetate fibers and film insolubility in aqueous alkali, makes it unacceptable for use as a size in a water jet weaving process.

EXAMPLE 17 In this example dibutyl maleate is used in place of the dimethyl maleate and diethyl maleate used in Examples 1 to above. The general polymerization procedures used in Example 1 are followed here using 91 .65 percent by weight of vinyl acetate, 5.0 percent by weight of dibutyl maleate and 3.35 percent by weight of acrylic acid. The resulting polymer has a specific viscosity of l.79, tensile strength of 2,050 psi dry and 680 psi wet'and elongation of 230 percent dry and 240 percent wet. The low wet tensile strength of this polymer makes it unacceptable for use as a size in a water jet weaving process.

EXAMPLE 18 EXAMPLE 19 In this example acrylonit'rile is used in place of the dimethylmaleate used in Examples l to 8 and 10. above. The general polymerization methods of Example 4 are followed using a monomer charge of percent by weight of vinyl acetate, 5 percent by weight of acrylic acid.

After 4 hours reaction time only 6.5 percent of the monomers have been converted into polymer.

EXAMPLE 20 I This example illustrates the criticality of using a surfactant which is a phosphate ester of an alkyl phenolethylene oxide condensate. Example 4 is repeated here except that octyl phenol-ethylene oxide condensate is used as the surfactant in place of the phosphate ester of octyl phenol-ethylene oxide condensate used in Example 4. The octyl phenol-ethylene oxide condensate used in this example is a well-known surfactant which is available commercially as Triton X-405 from Rohm and Haas. After 3 hours reaction time the batch was completely coagulated.

EXAMPLE 2;

Example 20 is repeated here exceptusing a surfactant which is a phosphate ester'of an aliphatic alcoholethylene oxide condensate. After 3 hours reaction time the batch was completely coagulated.

PART B TESTING OF THE LATlCES OF EXAMPLESl to 5 AND 7 to 10 AS TEXTlLE SIZES carbonate, ammonium bicarbonate, sodium hydroxide or sodium carbonate. Other basic solutions may be used to dissolve the latices as for example, aqueous solutions of alkali metal hydroxides, carbonates and bicarbonates as well' as aqueous solutions of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propyl amine, n-butyl amine, morpholine, etc. The sizing solutions contain between 1 and 25 percent solids. The concentration is readily selected by one skilled in the art so that the desired add-on to the yarns and solution viscosity for ease of application of the sizing solution are obtained.

The key properties considered in these tests are listed below? i Solubility all of the latices in question are soluble in aqueous bases such as aqueous ammonium hydroxide to provide sizing solutions. I Sizing Solutions prepared from the latices of Examples l to 5 and 7 to 10 have Brookfield viscosities in the range of from l to 300 centipoises at 4 to 5 percent solids allowing ease of application to the yarn. Wet Tensile Strength films prepared from the latices of the present invention have wet tensile strength in excess of l,000 psi and the necessary sion to the following yarns filaments, acetate, polyester, rayon, texturized polyester, nylon; spun polyester, cotton, rayon and wool; acetate, nylon and blends thereof.

Resolubility in mild alkali dried films of the latices in question are readily soluble in tetrasodium pyrophosphate surfactant solutions which indicates that the size is easily removed from the woven fabric. The size is also soluble in chlorinated solvents used in desizing operations.

Size efficiency is a measure of the amount of size add-on required in a given operation. The add-on is the amount of size that must be applied to the yarn in order to permit it to be woven on a water jet loom. In general, the less size add-on required, I

the more efficient the size. Sizes prepared from the latices of the present invention have excellent effiresulting latex, wherein the polymer component has aspecific viscosityof 2.7, is dissolved in aqueous ammonium hydroxide to give a 5.0 percent solids solution having a pH of 9.0.

This sizing solution at 120 F. is applied to a 150 denier, 41 monofilament, 10w twist bright acetate yarn on a commercial eleven can slasher at a rate of 90 yards per minute for a size add-on of 2.1 percent. Drying can temperatures on the slasher are 185l200l200l215/220/220/230/220/210/80/l- 30F. respectively. The split is very easy, and no ends break out at start-up.

The sized warp is entered into a Nissan Prince water jet loom, where at 400 picks per minute the weaving operation runs at very high efficiency, 98 percent) with no second quality fabric produced. The woven fabric has a dry" appearance in contrast to warps woven with lower M.W. (specific viscosity of 0.7) materials which become wet and slimy. Successive warps shows the same excellent performance. This fabric was desized in a conventional process by scouring in tetrasodium pyrophosphate wetting agent baths. The

size is also removable in a chlorinated solvent scouring process. 1

EXAMPLE 23 Example 22 is repeated here using a-latex with a specific viscosity of 2.73. This latex is dissolved with aqueous-ammonium hydroxide to give a 4.5 percent solids solution having a pH of 9.2. The size is applied to a denier 20 monofilament low twist (75/20/LT) bright acetate yarn on a seven can slasher. The slasher is run at 25 yards per minute at a size add-on of 1.9percent drying can temperatures of /170/210/160/190/150/cold, respectively. The lsplits very easily and weaves at very high efficiency to give good quality fabric which is desized as in Example 22.

EXAMPLE v24 This example is set forth 'to illustrate the exceptional efficiency of the sizes prepared according to the processes of the present invention. Example 22 is repeated here using a latex with a specific viscosity of 2.73. This latex is dissolved with aqueous ammonium hydroxide to give a 4.5 percent solids solution having a pH of 9.2. The size is applied to a 150 denier, 40 monofilament, 0.8 twist (150/40/0.8) bright acetate yarn on a seven can slasher at 55 yards per minute at a size add-on of 1.6 percent. Drying can temperatures are /2l0/210/2l0/ l90/coo1. The warp splits very easy, and no ends break out during the sizing operation. The warp weaves a very high efficiency to give good quality fabric which is desized as in Example 22. The add-on rate (1.6 percent) used in this example is unusually lowwhen compared to the sizes of the prior art which must be used in much larger amounts.

Sizes which are obtained from polymers prepared by the processes of the present invention are compared to commercially available textile sizes. The results of these comparisons is set forth below. In these tests the toughness value is the product of tensile times elongation.

Various sizes in the form of ammonium salts are applied to acetate and polyester filaments under jet conditions. The size is tested for wet tensile, wet elongation, wet toughness and wet adhesion. The results are tabulated in the following Table IV.

TABLE IV TESTS ON WATER JET SIZE ON ACETATE AND POLYESTER FILAMENT COMPOSITION SPECIFIC TENSILE TOUGHNESS ADHESION (2) SIZE (1) VISCOSITY (psi) ELONGA- (Xl0) ACETATE POLYESTER TlON A VA/DMM/AA 90.5/5/45 2.36 2150 540 116 Excellent Good 9l.65/5/3.35 1.79 700 250 17.5 Poor Poor C VA/CA 96/4 0.7 750 200 15 Good Good D VA/MMM 93/7 1.4 700 400 28 Fair Poor E VA/MIBM 79/21 1.9 60 540 3.2 Good Poor F VA/MA 47/53 0 0 Poor Poor G AA/AE 480 200 9.6 Good Excellent (1) Values are in weight percent.

VA vinyl acetate DMM dimethyl maleate DBM dibutyl maleate MMM monomethyl maleate MlBM monoisobutyl maleatc AA acrylic acid MA maleic anhydride AE acrylate ester (2) Qualitativu adhesion tests are run under wet conditions on fiber imhedded into size.

Size A is obtained from a latex that is prepared according to the processes of the present invention. Sizes C to G are commercially available sizes which are representative of the prior art. Note that Size A has good to excellent adhesion and is at least five times tougher than the sizes of the prior art.

I CONVENTIONAL SIZE ON ACETATE, RAYON AND TEXTURIZED POLYESTER Various sizes in the form of sodium salts are applied to filament acetate, rayon filament and texturized polyester. The sizes are then tested under conditions of 65 percent RH. for tensile, elongation, toughness and adhesion. The results are tabulated in the following Table V.

TABLE V CONVENTIONAL SIZE ON AC EI'ATE. RAYON AND TEXTURIZED POLYESTER 71 ADHESION (2) ELON- TOUGI-I- ACE- RAY- GATION NESS TATE ON TEN- SILE (psi) SIZE l t l Compositions A to F are the same as in Table IV above except that A has a specific viscosity of 2.94.

(I is a commercial gelatin sizc,

H is an equimolar styrene maleic unhydridc copolymer.

(3.) Numerical values are pounds required to break A: X '/4 inch lap joints. Size A, which is obtained from a latex prepared according to the processes of the present invention, ex-

hibits greater toughness and better adhesion than the sizes of the prior art.

LOOM FINISH ACETATE AND NYLON SIZES Various sizes in the form of ammonium salts are applied to acetate and nylon filament yarns. In the acetate application the size remains on the resulting fabric as a loom finish. Sizes used in this application must be very resistant to water spotting. The sizes are then tested under conditions of percent RH. for tensile, elongation, toughness and adhesion. The results are tabulated in the following Table VI."

TABLE VI LOOM FINISH ACETATE AND NYLON SIZES TEN- 7r TOUGH- ADHESION SIZE SILE ELON- NESS (lbs) (2) l (psi) GATION (X 10") ACETATE NYLON A 3450- 370 I28 I9 I3 B 2060 230 47 40 9 C I660 I30 22 27 I I D 2250 I60 36 I4 16 E 3830 20 8 I4 I l Poly- 2000 500 I00 15 vinyl Alcohol ( I) Compositions A to E same as in Table IV above except that A has a specific viscosity of 2.66. The polyvinyl alcohol used is a partially hydrolyzed low molecular weight polymer which cannot be used as a loom finish because of its water sensitivity. I

(2) Tested as in Table V.

Once again, Size A, which is representative of the sizes of the present invention, shows superior toughness. The adhesion of this size to acetate and nylon further indicateits utility as a textile size.

SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLE APPLICATIONS In certain applications it is desirable to size yarns such as cotton, rayon, wool, polyester and blends thereof and then remove the size from the resulting fabric using either aqueous alkali or an organic solvent. In the following tests various sizes are applied to polyester and then tested under conditions of percent RH. for tensile, elongation, toughness, adhesion and solubility. The test results are tabulated in the following Table VII.

TABLE VII SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLE APPLICATIONS I) Compositions A to E same as in Table IV above except that A has a specific viscosity of 3.71 and a VA/DMM/AA composition of l5/57r by weight.

PVOH-PH is a high molecular weight partially hydrolyzed polyvinyl alcohol.

PVOH-FH is a high molecular weight fully hydrolyzed polyvinyl alcohol.

CMC/Binder is a blend of carboxymethyl cellulose and an acrylate binder.

StarchfBinder is a blend of starch and an acrylate binder.

(2) Adhesion tests are run on a ,a square inch polyester to wood board bond.

(3) The aqueous solution contains a tetrasodium pyrophosphatc wetting agent combination.

The organic solvent usedis trichloroethylene.

Size A which is representative of the sizes of the present invention exhibits excellent toughness and adhesion. Moreover, this material is removable in conventional aqueous desizing operations as well as in organic solvent desizing operations. This latter feature is especially important where water shortages or water pollution problems exist.

Another feature of the present invention is the fact that the polymeric material may be dissolved in organic solvents to form a size. This feature is especially desirable in certain applications wherein solvent size removal techniques are also employed. In such applications the polymer solids are recovered from the latex, using conventional means. The polymer solids are then dissolved in an organic solvent to form the textile size and the size in the form of an organic solvent solution is applied. Size removal may be accomplished using aqueous alkali or organic solvent methods.

Preferred organic solvents used in preparing the sizes are alcohols, ketones, esters and aromatic solvents. Especially preferred are chlorinated aliphatic hydrocarbons such as methylene chloride, methylene bromide, chloroform, bromoform, ethylene dichloride, ethylene dibromide, ethylidene chloride, ethylidene bromidef s-tetrachloroethane, hexachloroethane, sdichloroethylene, l,1,-trichloroethane, 1,1,2- trichloroethane, trichloroethylene, trimethylene bromide, trichlorobromoethane, trichloromethane, 1,2,3- trichloropropane, l, l ,Z-trichloropropane, trifluoro- 1,2-tribromoethane, trifluoro l l ,Z-tribromoethane, trifluoro-l l ,2-trichloroethane, 2,2-dichlorol bromoethane, l,3-dichloro-Z-methyl-propane, l,2-dichloro-2-methylpropane, l,l-diiodoethane and the like. Chlorinated aliphatic liquid hydrocarbons are preferred in the practice of this invention because oftheir generally lower cost, greater availability and the ease with which these solvents may be handled.

From the foregoing, it should be obvious that many variations are possible in the present invention without departing from the spirit and scope thereof. Conventional adjuvants, lubricants, defoamers and plasticizers may be added without departing from the scope of the invention.

What is claimed is:

l. A method for sizing textile yarns to provide a water-resistant coating which comprises coating the textile yarn with a solution comprising the interpolymerization product of from 83 to 95 percent by weight of vinyl acetate, from 2 to percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, and drying the coated textile yarn to remove solvent.

2. The method of claim 1, wherein the solution comprises the interpolymerization product of from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl'maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers.

3. The method of claim 1, wherein the dialkyl maleate is dimethyl maleate.

'4. The method of claim 1, wherein the interpolymer I 8. A textile material coated with a size comprising an interpolymer of from 83 to percent by weight of vinly acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers.

9.The textile material of claim 8 coated with a size comprising an interpolymer of from 87.5 to 91 percent by-weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers.

10. The textile material of claim 8, wherein the dialkyl maleate is dimethyl maleate.

11. The textile material of claim 8, wherein the interpolymer has a specific viscosity when measured as a 1 percent solution in dimethysulfoxide at 20 C. in the range of from L2 to 12.

12. The textile material of claim 8 coated with a size comprising an interpolymer of from 87.5 to 91 percent I by weight of vinyl acetate, from 5 to 7.5 percent by weight of dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers; wherein the interpolymer has a specific viscosity when measured as a 1 percent solution in dimethyl sulfoxide at 20 C. in the range of from 1.2 to 12.

13. The textile material of claim 8 wherein the textile material is acetate filament, polyester filament, rayon filament, texturized polyester, texturized nylon, spun 

1. A METHOD FOR SIZING TEXTILE YARNS TO PROVIDE A WATERRESISTANT COATING WHICH COMPRISES COATING THE TEXTILE YARN WITH A SOLUTION COMPRISING THE INTERPOLYMERIZATION PRODUCT OF FROM 83 95 PERCENT BY WEIGHT OF VINYL ACETATE FROM 2 TO 10 PERCENT BY WEIGHT OF A DIALKYL MALEATE SELECTED FROM THE GROUP CONSISTING OF DIMETHYL MALEATE AND DIETHYL MALEATE AND FROM 3 TO7 PERCENT BY WEIGHT OF ACRYLIC ACID BASED ON THE TOTAL WEIGHT OF THE MONOMRS, AND DRYING THE COATED TEXTILE YARN TO REMOVE SOLVENT.
 2. The method of claim 1, wherein the solution comprises the interpolymerization product of from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers.
 3. The method of claim 1, wherein the dialkyl maleate is dimethyl maleate.
 4. The method of claim 1, wherein the interpolymer has a specific viscosity when measured as a 1 percent solution in dimethylsulfoxide at 20* C. in the range of from 1.2 to
 12. 5. The method of claim 1, wherein the size contains from 1 to 25 percent by weight of interpolymer based on the total weight of the solution.
 6. The method of claim 1, wherein the solvent portion of The solution is an aqueous base.
 7. The method of claim 1, wherein the solvent portion of the solution is a chlorinated aliphatic hydrocarbon solvent.
 8. A textile material coated with a size comprising an interpolymer of from 83 to 95 percent by weight of vinly acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers.
 9. The textile material of claim 8 coated with a size comprising an interpolymer of from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers.
 10. The textile material of claim 8, wherein the dialkyl maleate is dimethyl maleate.
 11. The textile material of claim 8, wherein the interpolymer has a specific viscosity when measured as a 1 percent solution in dimethysulfoxide at 20* C. in the range of from 1.2 to
 12. 12. The textile material of claim 8 coated with a size comprising an interpolymer of from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers; wherein the interpolymer has a specific viscosity when measured as a 1 percent solution in dimethyl sulfoxide at 20* C. in the range of from 1.2 to
 12. 13. The textile material of claim 8 wherein the textile material is acetate filament, polyester filament, rayon filament, texturized polyester, texturized nylon, spun polyester, cotton, rayon, or wool. 